CN103794478B - N-type diffusion layer is formed by composition, the manufacture method of n-type diffusion layer and the manufacture method of solar cell device - Google Patents

N-type diffusion layer is formed by composition, the manufacture method of n-type diffusion layer and the manufacture method of solar cell device Download PDF

Info

Publication number
CN103794478B
CN103794478B CN201410050927.6A CN201410050927A CN103794478B CN 103794478 B CN103794478 B CN 103794478B CN 201410050927 A CN201410050927 A CN 201410050927A CN 103794478 B CN103794478 B CN 103794478B
Authority
CN
China
Prior art keywords
diffusion layer
type diffusion
formation composition
layer formation
mole
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410050927.6A
Other languages
Chinese (zh)
Other versions
CN103794478A (en
Inventor
町井洋一
吉田诚人
野尻刚
岩室光则
织田明博
足立修一郎
佐藤铁也
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lishennoco Co ltd
Resonac Holdings Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of CN103794478A publication Critical patent/CN103794478A/en
Application granted granted Critical
Publication of CN103794478B publication Critical patent/CN103794478B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
    • H01L21/2251—Diffusion into or out of group IV semiconductors
    • H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides
    • H01L21/2255—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides the applied layer comprising oxides only, e.g. P2O5, PSG, H3BO3, doped oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
    • H01L21/2225—Diffusion sources
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1864—Annealing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electromagnetism (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Photovoltaic Devices (AREA)

Abstract

A kind of n-type diffusion layer formation composition, it comprises: containing P 2o 5, SiO 2and the glass powder of CaO, and decentralized medium.By this n-type diffusion layer formation composition to be coated on semiconductor substrate and to implement heat diffusion treatment, thus manufacture n-type diffusion layer and there is the solar cell device of n-type diffusion layer.

Description

N-type diffusion layer is formed by composition, the manufacture method of n-type diffusion layer and the manufacture method of solar cell device
The divisional application of the present invention's to be application number be patent of invention of 201280035500.8, parent application day is on July 17th, 2012, and female case denomination of invention is identical with above-mentioned title.
Technical field
The present invention relates to a kind of n-type diffusion layer formation composition of solar cell device, the manufacture method of n-type diffusion layer and the manufacture method of solar cell device.More specifically, the present invention relates to a kind of technology that can form n-type diffusion layer at the specific part of the silicon as semiconductor substrate.
Background technology
The manufacturing process of silicon solar cell element is in the past described.
First, in order to promote that light slumping is to seek high efficiency, prepare the p-type silicon substrate being formed with texture structure at sensitive surface, next, at the phosphorous oxychloride (POCl as the compound containing donor element 3), under the mixed-gas environment of nitrogen, oxygen, carry out the process of dozens of minutes with 800 DEG C ~ 900 DEG C and similarly form n-type diffusion layer.In this method in the past, because of the diffusion using mist to carry out phosphorus, so not only form n-type diffusion layer on surface, and in side, the back side also forms n-type diffusion layer.Therefore, the pullback step of the n-type diffusion layer for removing side is needed.In addition, the n-type diffusion layer at the back side must convert p to +type diffusion layer, n-type diffusion layer overleaf gives Aluminum Paste, converts p by the diffusion of aluminium to by n-type diffusion layer +type diffusion layer.
On the other hand, in the manufacture field of semiconductor, propose following method: as the compound containing donor element, coating is containing phosphorus pentoxide (P 2o 5) or ammonium dihydrogen phosphate (NH 4h 2pO 4) etc. phosphatic solution, form n-type diffusion layer (such as with reference to Japanese Unexamined Patent Publication 2002-75894 publication) thus.In addition, in order to form diffusion layer, coat containing the paste of phosphorus as donor element on silicon substrate as diffuse source, and carry out thermal diffusion to form the technology of diffusion layer also known (such as with reference to Japan Patent No. 4073968 publication).
Summary of the invention
Invent problem to be solved
But, in these methods, donor element or the compound containing it disperse from as the solution of diffuse source or paste, therefore identical with using the gas-phase reaction method of above-mentioned mist, when forming diffusion layer, phosphorus also diffuses to side and the back side, thus beyond be coated with part, also forms n-type diffusion layer.
Like this, when forming n-type diffusion layer, in the gas-phase reaction using phosphorous oxychloride, not only originally need the one side of n-type diffusion layer (being generally sensitive surface or surface) to form n-type diffusion layer, and also form n-type diffusion layer at another side (non-sensitive surface or the back side) or side.In addition, comprise the solution of compound containing phosphorus or paste in coating and make in the method for its thermal diffusion, identical with gas-phase reaction method, beyond surface, also form n-type diffusion layer.Therefore, for making element have pn junction structure, must etch in side, converting n-type diffusion layer to p-diffusion layer overleaf.Usually, be coated with the paste of the aluminium as the 13rd race's element overleaf, and burn till, thus convert n-type diffusion layer to p-diffusion layer.And then, previously known, the paste containing donor elements such as phosphorus is carried out in the method be coated with as diffuse source, compound containing donor element is vaporized gasification, also to needing the region of diffusion with outdiffusion, is therefore difficult to optionally form diffusion layer in specific region.
The present invention is the invention completed in view of above problem points in the past, its problem is to provide a kind of n-type diffusion layer formation composition, the manufacture method of n-type diffusion layer and the manufacture method of solar cell device, said n type diffusion layer formation composition can be applicable to the manufacture of the solar cell device employing semiconductor substrate, it can not form n-type diffusion layer in unwanted region, and can form n-type diffusion layer in specific region.
For solving the means of problem
The means solving above-mentioned problem are as follows.
<1> n-type diffusion layer formation composition, it comprises: containing P 2o 5, SiO 2and the glass powder of CaO; And decentralized medium.
The n-type diffusion layer formation composition of <2> as described in above-mentioned <1>, wherein, described glass powder contains more than 20 % by mole and the P of less than 50 % by mole 2o 5, more than 30 % by mole and the SiO of less than 70 % by mole 2, more than 2 % by mole and the CaO of less than 30 % by mole.
The n-type diffusion layer formation composition of <3> as described in above-mentioned <1> or <2>, wherein, the volume average particle size of described glass powder is less than 10 μm.
The n-type diffusion layer formation composition of <4> as described in any one in above-mentioned <1> ~ <3>, it comprises more than the 1 quality % of gross mass and the described glass powder of below 30 quality %.
The n-type diffusion layer formation composition of <5> as described in any one in above-mentioned <1> ~ <4>, its viscosity is more than 1Pas and below 500Pas.
The n-type diffusion layer formation composition of <6> as described in any one in above-mentioned <1> ~ <5>, wherein, described decentralized medium comprises at least a kind that is selected from terpineol and acetate of butyl carbitol.
The n-type diffusion layer formation composition of <7> as described in any one in above-mentioned <1> ~ <6>, wherein, described decentralized medium comprises ethyl cellulose.
The manufacture method of a <8> n-type diffusion layer, it comprises:
Give the operation of the n-type diffusion layer formation composition described in any one in above-mentioned <1> ~ <7> on a semiconductor substrate; And heat diffusion treatment is implemented to the semiconductor substrate being endowed n-type diffusion layer formation composition, thus form the operation of n-type diffusion layer.
The manufacture method of the n-type diffusion layer of <9> as described in above-mentioned <8>, wherein, the temperature of described heat diffusion treatment is 800 DEG C ~ 1000 DEG C.
The manufacture method of the n-type diffusion layer of <10> as described in above-mentioned <8> or <9>, it also comprises: before described heat diffusion treatment, with more than 80 DEG C and the temperature of less than 300 DEG C the semiconductor substrate being endowed n-type diffusion layer formation composition is heat-treated, thus by the operation removed at least partially of decentralized medium contained in this n-type diffusion layer formation composition.
The manufacture method of the n-type diffusion layer of <11> as described in any one in above-mentioned <8> ~ <10>, it also comprises: before described heat diffusion treatment, with more than 300 DEG C and the temperature of less than 800 DEG C the semiconductor substrate being endowed n-type diffusion layer formation composition is heat-treated, thus by the operation removed at least partially of decentralized medium contained in this n-type diffusion layer formation composition.
The manufacture method of the n-type diffusion layer of <12> as described in any one in above-mentioned <8> ~ <11>, it also comprises: after described heat diffusion treatment, utilizes the surface of hydrofluoric acid to the n-type diffusion layer formed on a semiconductor substrate to carry out the operation of etch processes.
The manufacture method of a <13> solar cell device, it comprises:
Give the operation of the n-type diffusion layer formation composition described in any one in above-mentioned <1> ~ <7> on a semiconductor substrate; Heat diffusion treatment is implemented to the semiconductor substrate being endowed n-type diffusion layer formation composition, thus forms the operation of n-type diffusion layer; And in formed n-type diffusion layer, form the operation of electrode.
The purposes of the n-type diffusion layer formation composition described in any one in the above-mentioned <1> ~ <7> of <14>, it is in the manufacture of n-type diffusion layer.
The purposes of the n-type diffusion layer formation composition described in any one in the above-mentioned <1> ~ <7> of <15>, it is used in the manufacture of solar cell device, and wherein this solar cell device comprises semiconductor substrate, n-type diffusion layer and electrode.
Invention effect
According to the present invention, a kind of n-type diffusion layer formation composition, the manufacture method of n-type diffusion layer and the manufacture method of solar cell device can be provided, said n type diffusion layer formation composition can be applicable to the manufacture of the solar cell device using semiconductor substrate, and it can not form n-type diffusion layer and forms n-type diffusion layer at specific area part in unwanted region.
Accompanying drawing explanation
Fig. 1 is the profile of an example of the manufacturing process conceptually representing solar cell device of the present invention.
Fig. 2 A is the plane graph of the viewed solar cell device from surface.
A part of Fig. 2 A is amplified the stereogram represented by Fig. 2 B.
Embodiment
First, n-type diffusion layer formation composition of the present invention is described, then the manufacture method of the n-type diffusion layer and solar cell device that use n-type diffusion layer formation composition is described.
In this manual, " operation " this term not only refers to independently operation, when being distinguished clearly with other operations, as long as reach the effect of the expection of this operation, is then also contained in this term.In addition, in this manual, number range represented by " ~ " is used to represent numerical value described in the front and back comprising " ~ " scope respectively as minimum value and maximum.And then, in this manual, the amount of each composition in composition when exist in the composition multiple be equivalent to the material of each composition time, as long as in advance without special instruction, then represent the total amount of the plurality of material existing in composition.
N-type diffusion layer formation composition of the present invention comprises at least containing P 2o 5, SiO 2and the glass powder of CaO (following, sometimes referred to as " glass powder "), and decentralized medium, and then consider the imparting adaptability (coating) etc. of composition, also can contain other additives as required.
Here, so-called n-type diffusion layer formation composition, refers to: comprise the glass powder containing donor element, and is made this donor element thermal diffusion can form the material of n-type diffusion layer by being imparted to after on semiconductor substrate.By using the n-type diffusion layer formation composition containing donor element in glass powder, n-type diffusion layer can be formed at desired position, not overleaf or side form unwanted n-type diffusion layer.
Therefore, if apply n-type diffusion layer formation composition of the present invention, then do not need necessary pullback step in the gas-phase reaction method previously extensively adopted, thus operation is simplified.In addition, do not need to convert the n-type diffusion layer being formed in the back side to p yet +the operation of type diffusion layer.Therefore, the p at the back side +the formation method of type diffusion layer, or the material of backplate, shape and thickness unrestricted, the selection degree of freedom of the manufacture method applied or material, shape expands.In addition, the generation of the internal stress in the semiconductor substrate caused by the thickness of backplate is inhibited, and the warpage of semiconductor substrate is also inhibited, and details is by aftermentioned.And then, also can form the selective emitting electrode structure making other parts of donor element concentration ratio immediately below electrode high.
It should be noted that, making glass powder melting contained in n-type diffusion layer formation composition of the present invention by burning till, glassy layer can be formed in n-type diffusion layer.But contain in the method for phosphatic solution or paste at gas-phase reaction method in the past or imparting, also form glassy layer in n-type diffusion layer, therefore, the glassy layer generated in the present invention can be removed by etching in the same manner as previous method.Therefore, even if compared with previous method, n-type diffusion layer formation composition of the present invention neither produces unwanted product, does not also increase operation.
In addition, even if the donor element in glass powder is also not easily vaporized in burning till, therefore not only form n-type diffusion layer on surface because being vaporized the generation of gas, even also overleaf or side form the situation of n-type diffusion layer and suppressed.As its reason, can think that donor element other elements in glass powder are combined or are fed in glass, therefore not easily be vaporized.
So, n-type diffusion layer formation composition of the present invention can form the n-type diffusion layer of desired concentration at desired position, therefore can form the optionally region that the concentration of N-shaped donor element (dopant) is high.But, usually pass through the gas-phase reaction method as the general method of n-type diffusion layer or the method for use containing phosphatic solution, be difficult to be formed the optionally region that the concentration of N-shaped donor element is high.
Glass powder of the present invention is described in detail.
Glass powder of the present invention comprises donor element.So-called donor element, refers to the element that can form n-type diffusion layer by spreading (doping) in semiconductor substrate.In the present invention, use P (phosphorus) as donor element.Use P 2o 5as the material containing donor element for donor element being directed in glass powder.
In addition, glass powder is at least containing SiO 2and CaO is as glass ingredient material.
Glass powder of the present invention is using the P as the material containing donor element 2o 5with the SiO as glass ingredient material 2and CaO is combined, thus moisture absorption is low, excellent storage stability.Therefore, even if after long-term preservation, the alms giver's composition in glass powder is also not easily vaporized in burning till, therefore because of be vaporized gas generation and not only on surface, even overleaf or the side situation that also forms n-type diffusion layer suppressed.
The ratio that contains of the material containing donor element in glass powder and glass ingredient material it is desirable to consider that melt temperature, softening temperature, glass transition temperature, chemical durability, etching characteristic etc. suitably set.Specifically, from the view point of resistance to water, melt temperature, diffusivity, P contained in glass powder 2o 5mole fraction be preferably 20 % by mole ~ 50 % by mole, be more preferably 25 % by mole ~ 45 % by mole.From the view point of resistance to water, melt temperature, etching characteristic, SiO 2mole fraction be preferably 30 % by mole ~ 70 % by mole, be more preferably 35 % by mole ~ 65 % by mole.From the view point of resistance to water, melt temperature, etching characteristic, the mole fraction of CaO is preferably 2 % by mole ~ 30 % by mole, is preferably 5 % by mole ~ 25 % by mole.
And then, by P in above-mentioned glass powder 2o 5with SiO 2and CaO and mole fraction is set to 100%, but in addition, also can comprise following glass ingredient material.As the glass ingredient material that can add, can enumerate: K 2o, Na 2o, Li 2o, BaO, SrO, MgO, BeO, ZnO, PbO, CdO, V 2o 5, SnO, ZrO 2, MoO 3, La 2o 3, Nb 2o 5, Ta 2o 5, Y 2o 3, TiO 2, ZrO 2, GeO 2, Al 2o 3, TeO 2and Lu 2o 3deng.As required to SiO 2and the component ratio of other glass ingredient materials beyond CaO adjusts, and can control melt temperature, softening temperature, glass transition temperature, chemical durability etc. thus.When glass powder comprises SiO 2and during glass ingredient material beyond CaO, from the view point of resistance to water, melt temperature, etching characteristic, diffusivity, can by SiO 2and the mole fraction of glass ingredient material in glass powder beyond CaO is set to 0.01 % by mole ~ 10 % by mole, is more preferably and is set to 0.1 % by mole ~ 5 % by mole.
From the view point of diffusivity during DIFFUSION TREATMENT, dropping liquid, the softening temperature of glass powder is preferably 300 DEG C ~ 1000 DEG C, is more preferably 400 DEG C ~ 900 DEG C.If softening temperature is more than 300 DEG C, then there is following tendency: during DIFFUSION TREATMENT, the viscosity of glass can not become too low, suppress the generation of dropping liquid, easily suppress the situation forming n-type diffusion layer beyond specific part.In addition, if less than 1000 DEG C, then there is following tendency: easily suppress glass powder incomplete fusion, and do not form the situation of uniform n-type diffusion layer.
By the softening temperature of glass powder being set in the scope of 300 DEG C ~ 1000 DEG C, as mentioned above, easily suppress the generation of dropping liquid, therefore after DIFFUSION TREATMENT, easily by n-type diffusion layer, desired shape is formed as to specific region.Such as when giving n-type diffusion layer formation composition with the linear pattern of a μm wide, the live width b after DIFFUSION TREATMENT can remain the linear pattern of the scope of b<1.5a μm.
The softening temperature of glass powder can use island Feng to make institute's (strain) and manufacture DTG-60H type differential thermogravimetric amount Simultaneously test device, and is obtained by differential heat (DTA) curve etc.
As the shape of glass powder, roughly spherical, flat, bulk, tabular and flakey etc. can be enumerated, from the imparting adaptability (coating) for substrate, even diffusible viewpoint when making n-type diffusion layer formation composition, it is desirable to roughly spherical, flat or tabular.
Glass powder preferred volume average grain diameter is less than 10 μm.When use has the glass powder of the volume average particle size of less than 10 μm, be easy to obtain level and smooth film.And then the volume average particle size of glass powder is more preferably less than 5 μm, more preferably less than 2 μm, be particularly preferably less than 1 μm.In addition, there is no particular restriction for the lower limit of the volume average particle size of glass powder, but be preferably 0.01 μmore than m, is more preferably more than 0.05 μm.
Here, the volume average particle size of glass powder measures by laser light scattering diffraction approach particle size distribution device etc.
Containing P 2o 5, SiO 2and the glass powder of CaO is by following sequentially built.
First raw materials weighing, and be filled in crucible.As the material of crucible, can enumerate: platinum, platinum-rhodium, gold, iridium, aluminium oxide, zirconia, quartz, carbon, boron carbide, boron nitride, silicon nitride etc.The material of crucible be consider melt temperature, environment, with the reactivity of melt substance etc. and suitablely to select.
Secondly, the temperature formed by electric furnace and to adapt to glass heats raw material, thus makes liquation.Now, it is desirable to carry out stirring to make liquation become even.
Next, the liquation of gained is made to flow out to liquation vitrifying on zirconia substrate or carbon base plate etc.
Finally, pulverize glass and formed Powdered.Pulverizing can apply the known methods such as bruisher, jet mill, ball mill, ball mill.
The diffusivity etc. containing ratio consideration imparting adaptability, donor element of the glass powder in n-type diffusion layer formation composition is determined.Generally speaking, the scope being preferably 1 quality % ~ 30 quality % containing ratio of the glass powder in n-type diffusion layer formation composition, is more preferably the scope of 5 quality % ~ 25 quality %, more preferably the scope of 8 quality % ~ 20 quality %.
From the view point of resistance to water, melt temperature, etching characteristic, diffusivity, the glass powder in the present invention can be the P of 20 % by mole ~ 50 % by mole containing mole fraction 2o 5, mole fraction is the SiO of 30% ~ 70% 2, and mole fraction be the CaO of 5 % by mole ~ 25 % by mole, and volume average particle size is 0.01 μm ~ 2 μm, or can be the P of 20 % by mole ~ 50 % by mole containing mole fraction 2o 5, mole fraction is the SiO of 35% ~ 65% 2, and mole fraction be the CaO of 2 % by mole ~ 30 % by mole, and volume average particle size is 0.01 μm ~ 2 μm, in addition, from the view point of resistance to water, melt temperature, etching characteristic, diffusivity, can be the P of 25 % by mole ~ 45 % by mole containing mole fraction 2o 5, mole fraction is the SiO of 30% ~ 70% 2, and mole fraction be the CaO of 2 % by mole ~ 30 % by mole, and volume average particle size is 0.01 μm ~ 2 μm.
From the view point of resistance to water, melt temperature, etching characteristic, diffusivity, it is the P of 25 % by mole ~ 45 % by mole that the glass powder in the present invention is more preferably containing mole fraction 2o 5, mole fraction is the SiO of 35% ~ 65% 2, and mole fraction be the CaO of 5 % by mole ~ 25 % by mole, and volume average particle size is 0.01 μm ~ 2 μm.
Then, decentralized medium is described.
So-called decentralized medium, refers to the medium making above-mentioned glass powder disperse in the composition.Specifically, be selected from the group be made up of binding agent and solvent at least a kind is adopted as decentralized medium.
As binding agent, such as can enumerate: polyvinyl alcohol, polyacrylamide resin, polyvinyl lactam resin, polyvinylpyrrolidone, polyethylene oxide resin, poly-sulfonic acid, acrylamide alkyl sulfonic acid, cellulose ether resins, cellulose derivative, carboxymethyl cellulose, hydroxyethylcellulose, ethyl cellulose, gelatin, starch and starch derivatives, sodium alginate and sodium alginate derivative, xanthans and xanthan derivatives, guar gum and guar derivative, scleroglucan and scleroglucan derivative, bassora gum and bassora gum derivative, dextrin and dextrin derivative, (methyl) acrylic resin, (methyl) acrylate (such as (methyl) acid alkyl ester resin, (methyl) dimethylaminoethyl acrylate resin etc.), butadiene resin, styrene resin, and their copolymer.In addition, suitably silicone resin can be selected in addition.These binding agents can be used alone a kind or two or more combinationally used.Wherein, from the view point of viscosity characteristics, as binding agent, preferred, ethyl.
There is no particular restriction for the molecular weight of binding agent, it is desirable to suitably adjust in view of as the viscosity desired by composition.In addition, as long as the ratio that contains of the binding agent in composition is set to the amount such as reaching following viscosity.
Consider imparting characteristic during printing, the viscosity of n-type diffusion layer formation composition is preferably the scope of 1Pas ~ 500Pas, is more preferably the scope of 10Pas ~ 100Pas.
Use the E type viscosimeter EHD type that Tokyo gauge manufactures in the mensuration of viscosity, sample size be 0.4ml, rotating speed measures under being the condition of 5rpm.
As solvent, such as can enumerate: the ketone solvents such as acetone, methyl ethyl ketone, methyl n-pro-pyl ketone, methyl isopropyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone, methyl n hexyl ketone, metacetone, dipropyl ketone, DIBK, trimethyl nonanone, cyclohexanone, cyclopentanone, methyl cyclohexanone, 2,4-pentanediones, acetonyl acetone, diethyl ether, methyl ethyl ether, methyl n-propyl ether, diisopropyl ether, oxolane, methyltetrahydrofuran, diox, dimethyl dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol bisthioglycolate positive propyl ether, butyl cellosolve, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl n-propyl ether, diethylene glycol methyl n-butyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, diethylene glycol methyl n-hexyl ether, TRIGLYME, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol methyl n-butyl ether, triethylene glycol di-n-butyl ether, triethylene glycol methyl n-hexyl ether, tetraethyleneglycol dimethyl ether, TEG diethyl ether, TEG methyl ethyl ether, TEG methyl n-butyl ether, diethylene glycol di-n-butyl ether, TEG methyl n-hexyl ether, TEG di-n-butyl ether, Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol butyl oxide, dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethylether, dipropylene glycol methyl n-butyl ether, DPG di-n-propyl ether, DPG di-n-butyl ether, dipropylene glycol methyl n-hexyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol methyl n-butyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol methyl n-hexyl ether, four Propylene Glycol Dimethyl Ether, four propylene glycol diethyl ether, four propylene glycol methyl ethyl ethers, four propylene glycol methyl n-butyl ethers, DPG di-n-butyl ether, four propylene glycol methyl n-hexyl ethers, the ether solvents such as four propylene glycol di-n-butyl ethers, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, acetic acid 3-methoxybutyl, methyl amyl acetate, acetic acid 2-ethyl butyl ester, acetic acid 2-Octyl Nitrite, acetic acid 2-(2-Butoxyethoxy) ethyl ester, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, dipropylene glycol monomethyl ether acetic acid esters, DPE acetic acid esters, ethylene acetate, methoxy triethylene acetic acid esters, ethyl propionate, n-butyl propionate, isoamyl propionate, diethy-aceto oxalate, dibutyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, N_amyl lactate, glycol monoethyl ether propionic ester, ethylene glycol monoethyl ether propionic ester, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, gamma-butyrolacton, the ester solvents such as gamma-valerolactone, acetonitrile, 1-METHYLPYRROLIDONE, N-ethyl pyrrolidone, N-propyl pyrrole alkane ketone, N-butyl pyrrolidine ketone, N-hexyl pyrrolidones, N-cyclohexyl pyrrolidone, N, dinethylformamide, N, the aprotic polar solvent such as N-dimethylacetylamide, N, N-dimethyl sulfoxide (DMSO), methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, 2-methyl butanol, sec-amyl alcohol, tert-pentyl alcohol, 3-methoxybutanol, n-hexyl alcohol, 2-methyl anyl alcohol, secondary hexyl alcohol, 2-ethyl butanol, secondary enanthol, n-octyl alcohol, 2-Ethylhexyl Alcohol, sec-octyl alcohol, n-nonyl alcohol, Decanol, secondary undecyl alcohol, Exxal 12, secondary tetradecyl alchohol, secondary heptadecanol, phenol, cyclohexanol, methyl cyclohexanol, benzylalcohol, ethylene glycol, 1, 2-propylene glycol, 1, 3-butanediol, diethylene glycol, DPG, triethylene glycol, the alcoholic solvents such as tripropylene glycol, the glycol monoethers solvents such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethyleneglycol monophenylether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol list n-hexyl ether, Triethylene glycol ethyl ether, TEG mono-n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, DPE, Tripropylene glycol monomethyl Ether, the terpene solvents such as α-terpinenes, terpineol, oreodaphene alkene, alloocimene, citrene, dipentene, australene, nopinene, terpinol, carvol, ocimenum, phellandrene, water etc.These solvents can be used alone a kind or two or more combinationally used.
From to the adaptive viewpoint of the imparting of substrate, in n-type diffusion layer formation composition, solvent is preferably selected from least a kind in terpineol and acetate of butyl carbitol (diethylene glycol mono-n-butyl ether acetic acid esters).Deciding containing ratio consideration imparting adaptability, donor concentration of decentralized medium in n-type diffusion layer formation composition.
Next, the manufacture method of n-type diffusion layer of the present invention and the manufacture method of solar cell device are described.
The manufacture method of n-type diffusion layer of the present invention comprises: the operation of giving above-mentioned n-type diffusion layer formation composition on a semiconductor substrate; And heat diffusion treatment is implemented to the semiconductor substrate being endowed n-type diffusion layer formation composition, thus form the operation of n-type diffusion layer.
The manufacture method of solar cell device of the present invention comprises: the operation of giving above-mentioned n-type diffusion layer formation composition on a semiconductor substrate; Heat diffusion treatment is implemented to the semiconductor substrate being endowed n-type diffusion layer formation composition, thus forms the operation of n-type diffusion layer; And in formed n-type diffusion layer, form the operation of electrode.
Below, reference Fig. 1 is while be described.Fig. 1 is the constructed profile of an example of the manufacturing process conceptually representing solar cell device of the present invention.In addition, in Fig. 1,10 represent p-type semiconductor substrate, and 12 represent n-type diffusion layer, and 14 represent p +type diffusion layer, 16 represent anti-reflective film, 18 presentation surface electrodes, and 20 represent backplate (electrode layer).In figures in the following, to identical inscape mark prosign, and omit the description.It should be noted that, although be described employing the example of silicon substrate as p-type semiconductor substrate below, in the present invention, semiconductor substrate is not limited to silicon substrate.
In Fig. 1 (1), give alkaline solution to the silicon substrate as p-type semiconductor substrate 10 and remove damage layer, and obtain texture structure by etching.
Specifically, 20 quality % caustic soda are utilized to remove the damage layer of the silicon face produced when silicon ingot is cut into slices.Next, utilize the mixed liquor of 1 quality % caustic soda and 10 quality % isopropyl alcohols to etch, thus form the texture structure record of omit texture structure (in the figure).Solar cell device by forming texture structure in sensitive surface (surface) side, and promotes light slumping, can seek high efficiency.
In Fig. 1 (2), namely the surface that said n type diffusion layer formation composition is imparted to p-type semiconductor substrate 10 is become on the face of sensitive surface, form n-type diffusion layer and formed with composition layer 11.In the present invention, adding method is also unrestricted, can enumerate print process, spin-coating method, hairbrush coating, spray-on process, scrape the skill in using a kitchen knife in cookery, roll coater method, ink-jet method, preferably print process, particularly silk screen print method.
As the imparting amount of said n type diffusion layer formation composition, there is no particular restriction, such as, as glass powder amount, can be set to 0.01g/m 2~ 100g/m 2, be preferably 0.1g/m 2~ 10g/m 2.
According to the composition of n-type diffusion layer formation composition, sometimes following operation is needed: before heat diffusion treatment, in order to the removal at least partially by solvent contained in composition, the substrate after imparting n-type diffusion layer formation composition is heat-treated.Heat treatment is now suitable for following condition: more than 80 DEG C and the temperature of less than 300 DEG C, carries out 1 minute ~ 10 minutes when using heating plate, carries out 10 minutes ~ about 30 minutes when using drying machine etc.This heat-treat condition depends on the solvent composition of n-type diffusion layer formation composition, is not particularly limited to above-mentioned condition in the present invention.By this heat treatment step, the n-type diffusion layer formation composition dries be imparted on substrate can be made.
In addition, according to the composition of n-type diffusion layer formation composition, sometimes following operation is needed: before heat diffusion treatment, in order to make decentralized medium contained in said composition at least partially, particularly binding agent (resinous principle) volatilizees thus is removed, and heat-treats the substrate after imparting n-type diffusion layer formation composition.Heat treatment is now suitable for following condition: at the temperature of less than 800 DEG C, carrying out the process of 1 minute ~ 10 minutes more than 300 DEG C.This heat treatment can apply known continuous oven, batch furnace etc.
When carrying out above-mentioned heat treatment, according to the composition of n-type diffusion layer formation composition, above-mentioned more than 80 DEG C and heat treatment at the temperature of less than 300 DEG C can be made, and (namely the heat treatment more than 300 DEG C and at the temperature of less than 800 DEG C all carried out, 2 heat treatment is carried out at different temperature conditions), also only can carry out the heat treatment at one of them temperature.
When using manufacture method of the present invention, the p at the back side +the manufacture method of type diffusion layer (high concentration electric field layer) 14 is not limited to the method for the conversion from the n-type diffusion layer formed by aluminium to p-diffusion layer, also can adopt known any method, and the selection degree of freedom of manufacture method expands.Therefore, the composition such as can giving the element containing the 13rd races such as B (boron), to form composition layer 13, then forms p +type diffusion layer 14.
As the composition of the above-mentioned element containing the 13rd races such as B (boron), include, for example the glass powder that the glass powder used containing recipient element replaces containing donor element, and with the p-diffusion layer formation composition that the mode identical with n-type diffusion layer formation composition is formed.As long as the element of recipient element the 13rd race, include, for example B (boron), Al (aluminium) and Ga (gallium) etc.In addition, the glass powder containing recipient element preferably comprises and is selected from B 2o 3, Al 2o 3and Ga 2o 3in at least a kind.
And then method p-diffusion layer formation composition being imparted to the back side of silicon substrate is identical with the above-mentioned method be imparted on silicon substrate by n-type diffusion layer formation composition.
In the mode identical with the heat diffusion treatment of n-type diffusion layer formation composition described later, heat diffusion treatment is carried out to the p-diffusion layer formation composition being imparted to the back side, p can be formed overleaf thus +type diffusion layer 14.It should be noted that, preferably, the heat diffusion treatment of p-diffusion layer formation composition and the heat diffusion treatment of n-type diffusion layer formation composition are carried out simultaneously.
Next, heat diffusion treatment is carried out to the p-type semiconductor substrate 10 being formed with said n type diffusion layer formation composition layer 11.Treatment temperature is preferably 800 DEG C ~ 1000 DEG C, is more preferably 850 DEG C ~ 980 DEG C.Processing time is preferably 5 minutes ~ 60 minutes.By this heat diffusion treatment, as shown in Fig. 1 (3), donor element spreads in semiconductor substrate, thus forms n-type diffusion layer 12.Heat diffusion treatment can apply known continuous oven, batch furnace etc.In addition, furnace inner environment during heat diffusion treatment also can suitably be adjusted to air, oxygen, nitrogen etc.
The glassy layers such as phosphoric acid glass (not shown) are formed on the surface of formed n-type diffusion layer 12.Therefore, this phosphoric acid glass is removed by etching.Etching can apply any one known method such as the method in acid such as impregnated in hydrofluoric acid, the method that impregnated in the alkali such as caustic soda, from the view point of etch capabilities, preferably utilizes the etch processes of hydrofluoric acid.When using the engraving method that impregnated in the acid such as hydrofluoric acid, there is no particular restriction for dip time, usually can be set to 0.5 minute ~ 30 minutes, is preferably set to 1 minute ~ 10 minutes.
In the formation method of the n-type diffusion layer of the present invention shown in Fig. 1 (2) and (3), desired position formed n-type diffusion layer 12, not overleaf or side form unwanted n-type diffusion layer.
Therefore, being formed in the method for n-type diffusion layer what extensively adopted in the past by gas-phase reaction method, needing the pullback step for removing the unwanted n-type diffusion layer being formed in side, but manufacturing method according to the invention, do not need pullback step, thus operation is simplified.Thus, by manufacture method of the present invention, the uniform n-type diffusion layer of desired shape can be formed at short notice at desired position.
In addition, in manufacture method in the past, must the unwanted n-type diffusion layer being formed in the back side be converted to p-diffusion layer, as this conversion method, adopt following method: paste n-type diffusion layer being overleaf coated with the aluminium as the 13rd race's element, and burn till, make aluminium diffuse to n-type diffusion layer thus convert n-type diffusion layer to p-diffusion layer.In the method, in order to convert n-type diffusion layer to p-diffusion layer fully, and then form p +the high concentration electric field layer of type diffusion layer, and need aluminum amount above to a certain degree, therefore must aluminium lamination be formed thick.But the thermal coefficient of expansion of aluminium differs widely with the thermal coefficient of expansion of the silicon being used as substrate, therefore in the process burnt till and cool, produces larger internal stress in silicon substrate, becomes the reason of the warpage of silicon substrate.
There is the crystal boundary of this internal stress to crystallization and cause damage, power loss change this problem large.In addition, the conveyance of the solar cell device of warpage in module operation or be called as in the connection procedure of copper cash of lug line (Wiring member), easily make solar cell device damaged.In recent years, due to the raising of slicing technology, thus there is the tendency that solar cell device is more prone to break in the therefore thickness of silicon substrate more and more slimming.
But manufacturing method according to the invention, owing to not forming unwanted n-type diffusion layer overleaf, therefore without the need to carrying out the conversion from n-type diffusion layer to p-diffusion layer, and need not make aluminium lamination thickening.Its result, can suppress generation or the warpage of the internal stress in silicon substrate.As a result, the increase of power loss or the breakage of solar cell device can be suppressed.
In addition, when using manufacture method of the present invention, the p at the back side +the manufacture method of type diffusion layer (high concentration electric field layer) 14 is not limited to the method for the conversion from the n-type diffusion layer formed by aluminium to p-diffusion layer, also can adopt any method, and the selection degree of freedom of manufacture method expands.
Preferably, such as replace the glass powder containing donor element and use the glass powder containing recipient element, and the back side (be the face of opposition side with the face imparting n-type diffusion layer formation composition) of silicon substrate is imparted to the p-diffusion layer formation composition that the mode identical with n-type diffusion layer formation composition is formed, and carry out burning till process, form p overleaf thus +type diffusion layer (high concentration electric field layer) 14.
In addition, as described later, the material for backplate 20 is not limited to the aluminium of the 13rd race, such as, can apply Ag (silver) or Cu (copper) etc., and the thickness of backplate 20 also can than the more unfertile land formation of thickness in the past.
In Fig. 1 (4), n-type diffusion layer 12 forms anti-reflective film 16.Anti-reflective film 16 is applied known technology to be formed.Such as, when anti-reflective film 16 is silicon nitride film, by by SiH 4with NH 3mist formed as plasma activated chemical vapour deposition (ChemicalVaporDeposition, the CVD) method of raw material.Now, hydrogen spreads in crystallization, does not participate in the track of the Cheng Jian of silicon atom, i.e. dangling bonds and hydrogen bonding, thus makes defect passivation (hydrogen passivation).
More specifically, formed under the following conditions: above-mentioned mixed gas flow compares NH 3/ SiH 4be 0.05 ~ 1.0, the pressure of reative cell is 13.3Pa (0.1Torr) ~ 266.6Pa (2Torr), and temperature during film forming is 300 DEG C ~ 550 DEG C, and the frequency for the electric discharge of plasma is more than 100kHz.
In Fig. 1 (5), on the anti-reflective film 16 on surface (sensitive surface), print coating surface electrode metal paste by silk screen print method and make it dry, thus forming surface electrode metal paste oxidant layer 17.Surface electrode by metal paste by (1) metallic and (2) glass particle as required composition, and comprise (3) resinoid bond, (4) other additives as required.
Next, at the p at the above-mentioned back side +type diffusion layer 14 is also formed backplate metal paste oxidant layer 19.As mentioned above, in the present invention, the material of backplate metal paste oxidant layer 19 or formation method are not particularly limited.Such as, the backplate paste comprising the metals such as aluminium, silver, copper can be given, and make its drying to form backplate metal paste oxidant layer 19.Now, in order to the connection between the solar cell device in module operation, also a part overleaf can be arranged silver electrode and be formed and use silver-colored paste.
In Fig. 1 (6), electrode metal paste oxidant layer 17 is burnt till and makes solar cell device.If burn till several seconds ~ a few minutes in the scope of 600 DEG C ~ 900 DEG C, then in face side, as anti-reflective film 16 melting because of glass particle contained in electrode metal paste of dielectric film, and then a part also melting on p-type semiconductor substrate 10 surface, the metallic (such as silver particles) in paste and p-type semiconductor substrate 10 form contact site and solidify.Thus, the surface electrode 18 formed is switched on p-type semiconductor substrate 10.This is called and burns logical (firethrough).In addition, side overleaf, burns till the backplate metal paste of backplate metal paste oxidant layer 19 similarly, thus forms backplate 20.
Shape with reference to Fig. 2 effects on surface electrode 18 is described.In addition, in fig. 2,30 represent bus electrode, and 32 represent finger electrode.The finger electrode 32 that surface electrode 18 comprises bus electrode 30 and intersects with this bus electrode 30.Fig. 2 A be from surface observation to plane graph surface electrode 18 being set to the solar cell device of the formation of the finger electrode 32 comprising bus electrode 30 and intersect with this bus electrode 30, a part of Fig. 2 A is amplified the stereogram represented by Fig. 2 B.
Such surface electrode 18 is formed by the method such as evaporation of the electrode material utilizing electron beam to heat in the plating of the silk screen printing of such as above-mentioned metal paste or electrode material, high vacuum.The electrode that the surface electrode 18 comprising bus electrode 30 and finger electrode 32 is typically used as sensitive surface side is known, can apply the bus electrode of sensitive surface side and the known formation method of finger electrode.
Hereinbefore, form n-type diffusion layer on surface, form p overleaf +type diffusion layer, and then the solar cell device being provided with surface electrode and backplate on each layer is illustrated, if but use n-type diffusion layer formation composition of the present invention, then also can make the solar cell device of rear-face contact type.
The solar cell device of rear-face contact type electrode is all arranged on the back side to increase the solar cell device of the area of sensitive surface.That is, in the solar cell device of contact-type overleaf, N-shaped diffusion position and p must be formed overleaf +type diffusion both positions become pn connected structure.N-type diffusion layer formation composition of the present invention can form N-shaped diffusion position at specific position, therefore compatibly can be applied in the manufacture of the solar cell device of rear-face contact type.
The purposes of said n type diffusion layer formation composition when manufacturing n-type diffusion layer and the purposes of said n type diffusion layer formation composition when manufacturing the solar cell device containing above-mentioned semiconductor substrate and n-type diffusion layer and electrode is also comprised respectively in the present invention.As mentioned above, the n-type diffusion layer formation composition of the application of the invention, unwanted n-type diffusion layer can not be formed and obtain uniform n-type diffusion layer in specific region with desired shape at short notice, in addition, unwanted n-type diffusion layer can not be formed and obtain the solar cell device with such n-type diffusion layer.
Embodiment
Below, further illustrate embodiments of the invention, but the present invention does not limit by these embodiments.In addition, as long as no special instructions, then chemicals all employs reagent.In addition, as long as in advance without illustrating, then " % " expression " quality % ".
[embodiment 1]
Use the P that shape of particle is bulk by automatic mortar kneading device, volume average particle size is 0.89 μm 2o 5-SiO 2-CaO system glass (P 2o 5: 30 % by mole, SiO 2: 60 % by mole, CaO:10 % by mole) powder 10g, ethyl cellulose 5g and terpineol 85g mix and carried out paste, thus having prepared n-type diffusion layer formation composition.The viscosity of the n-type diffusion layer formation composition of gained is 61Pas.
In addition, glass particle shape is that the TM-1000 type scanning electron microscope using HitachiHigh-Technologies (strain) to manufacture carries out observing and judging.The average grain diameter of glass is that the LS13320 type laser light scattering diffraction approach particle size distribution device (measuring wavelength: 632nm) using BeckmanCoulter (strain) to manufacture calculates.
The viscosity of n-type diffusion layer formation composition is the E type viscosimeter EHD type using Tokyo gauge to manufacture, sample size be 0.4ml, rotating speed is that the condition of 5rpm measures.
In addition, use the DTG-60H type differential thermogravimetric amount Simultaneously test device that island Feng making institute (strain) manufactures, and obtained the softening temperature of glass by differential heat (DTA) curve, result can be speculated as near 800 DEG C.
Then, by silk screen printing, prepared paste is coated on the surface of p-type silicon substrate, and on the heating plate of 150 DEG C dry 5 minutes and form layer.Next, carry out heat treatment in 5 minutes being set in the electric furnace of 500 DEG C, next be set to 950 DEG C diffusion other electric furnaces in carry out 10 minutes heat diffusion treatment.Then, in order to remove glassy layer, substrate being flooded 5 minutes in hydrofluoric acid, then having carried out flowing water cleaning and drying.
The film resistor being coated with the surface of the side of n-type diffusion layer formation composition is 45 Ω/, P (phosphorus) diffusion and defines n-type diffusion layer.The film resistor at the back side is more than determination of the upper limit and cannot measures, and does not form n-type diffusion layer.
It should be noted that, film resistor is the Loresta-EPMCP-T360 type low-resistivity meter using Mitsubishi Chemical's (strain) to manufacture, and is measured at 25 DEG C by four probe method.
[embodiment 2]
Use the P that shape of particle is bulk by automatic mortar kneading device, volume average particle size is 0.95 μm 2o 5-SiO 2-CaO system glass (P 2o 5: 30 % by mole, SiO 2: 50 % by mole, CaO:20 % by mole) powder 10g, ethyl cellulose 5g and acetate of butyl carbitol 85g mix and carried out paste, thus having prepared n-type diffusion layer formation composition.The viscosity of the n-type diffusion layer formation composition of gained is 67Pas.
Next, by silk screen printing, prepared paste is coated the surface of p-type silicon substrate, and on the heating plate of 150 DEG C dry 5 minutes, thus form layer.Next, carry out heat treatment in 5 minutes being set in the electric furnace of 500 DEG C, next be set to 950 DEG C diffusion other electric furnaces in carry out 10 minutes heat diffusion treatment.Subsequently, in order to remove glassy layer, substrate being flooded 5 minutes in hydrofluoric acid, then having carried out flowing water cleaning and drying.
The film resistor being coated with the surface of the side of n-type diffusion layer formation composition is 38 Ω/, P (phosphorus) diffusion and defines n-type diffusion layer.The film resistor at the back side is more than determination of the upper limit and cannot measures, and does not form n-type diffusion layer.
[embodiment 3]
Use automatic mortar kneading device to be roughly spherical, volume average particle size by shape of particle to be the P of 1.02 μm 2o 5-SiO 2-CaO system glass (P 2o 5: 40 % by mole, SiO 2: 40 % by mole, CaO:20 % by mole) powder 10g, ethyl cellulose 5g and acetate of butyl carbitol 85g mix and carried out paste, thus having prepared n-type diffusion layer formation composition.The viscosity of the n-type diffusion layer formation composition of gained is 65Pas.
Next, by silk screen printing, prepared paste is coated the surface of p-type silicon substrate, and on the heating plate of 150 DEG C dry 5 minutes, thus form layer.Next, carry out heat treatment in 5 minutes being set in the electric furnace of 500 DEG C, next be set to 950 DEG C diffusion other electric furnaces in carry out 10 minutes heat diffusion treatment.Subsequently, in order to remove glassy layer, substrate being flooded 5 minutes in hydrofluoric acid, then having carried out flowing water cleaning and drying.
The film resistor being coated with the surface of the side of n-type diffusion layer formation composition is 35 Ω/, P (phosphorus) diffusion and defines n-type diffusion layer.The film resistor at the back side is more than determination of the upper limit and cannot measures, and does not form n-type diffusion layer.
[comparative example 1]
Use automatic mortar kneading device by ammonium dihydrogen phosphate (NH 4h 2pO 4) powder 10g, ethyl cellulose 5g and terpineol 85g mix and have carried out paste, prepared n-type diffusion layer composition.
Next, by silk screen printing, prepared paste is coated the surface of p-type silicon substrate, and on the heating plate of 150 DEG C dry 5 minutes and form layer.Next, carry out heat treatment in 5 minutes being set in the electric furnace of 500 DEG C, next be set to 950 DEG C diffusion other electric furnaces in carry out 10 minutes heat diffusion treatment.Subsequently, in order to remove glassy layer, substrate being flooded 5 minutes in hydrofluoric acid, then having carried out flowing water cleaning and drying.
The film resistor being coated with the surface of the side of n-type diffusion layer formation composition is 51 Ω/, P (phosphorus) diffusion and defines n-type diffusion layer.But the film resistor at the back side is 60 Ω/, is also formed with n-type diffusion layer overleaf.
[comparative example 2]
Use automatic mortar kneading device by ammonium dihydrogen phosphate (NH 4h 2pO 4) powder 1g, pure water 7g, polyvinyl alcohol 0.7g and isopropyl alcohol 1.5g mixing prepares solution, thus prepared n-type diffusion layer composition.
Next, by spin coater (2000rpm, 30sec) by the surface of prepared solution coat in p-type silicon substrate, and on the heating plate of 150 DEG C dry 5 minutes and form layer.Next, carry out heat treatment in 5 minutes being set in the electric furnace of 500 DEG C, next be set to 950 DEG C diffusion other electric furnaces in carry out 10 minutes heat diffusion treatment.Subsequently, in order to remove glassy layer, substrate being flooded 5 minutes in hydrofluoric acid, then having carried out flowing water cleaning and drying.
The film resistor being coated with the surface of the side of n-type diffusion layer formation composition is 43 Ω/, P (phosphorus) diffusion and defines n-type diffusion layer.But the film resistor at the back side is 55 Ω/, is also formed with n-type diffusion layer overleaf.
By referring to and full content disclosed in No. 2011-158489, Japanese patent application being applied on July 19th, 2011 is introduced in this specification.
All documents described in this specification, patent application and technical specification be with particularly and record respectively by referring to and introduce each document, the situation of patent application and technical specification is identical degree, by referring to and be introduced in this specification.

Claims (10)

1. a n-type diffusion layer formation composition, it comprises: containing P 2o 5, SiO 2and the glass powder of CaO; And decentralized medium, its viscosity is more than 1Pas and below 500Pas.
2. n-type diffusion layer formation composition as claimed in claim 1, wherein, described glass powder contains more than 20 % by mole and the P of less than 50 % by mole 2o 5, more than 30 % by mole and the SiO of less than 70 % by mole 2, more than 2 % by mole and the CaO of less than 30 % by mole.
3. n-type diffusion layer formation composition as claimed in claim 1, wherein, the volume average particle size of described glass powder is less than 10 μm.
4. n-type diffusion layer formation composition as claimed in claim 1, it comprises more than the 1 quality % of gross mass and the described glass powder of below 30 quality %.
5. n-type diffusion layer formation composition as claimed in claim 1, wherein, described decentralized medium comprises at least a kind that is selected from terpineol and acetate of butyl carbitol.
6. n-type diffusion layer formation composition as claimed in claim 1, wherein, described decentralized medium comprises ethyl cellulose.
7. a manufacture method for n-type diffusion layer, it comprises:
Entitle requires the operation of the n-type diffusion layer formation composition described in 1 on a semiconductor substrate; And
Heat diffusion treatment is implemented to the semiconductor substrate being endowed n-type diffusion layer formation composition, thus forms the operation of n-type diffusion layer,
Also comprise: before described heat diffusion treatment, with more than 300 DEG C and the temperature of less than 800 DEG C the semiconductor substrate being endowed n-type diffusion layer formation composition is heat-treated, thus by the operation removed at least partially of decentralized medium contained in this n-type diffusion layer formation composition.
8. the manufacture method of n-type diffusion layer as claimed in claim 7, wherein, the temperature of described heat diffusion treatment is 800 DEG C ~ 1000 DEG C.
9. the manufacture method of n-type diffusion layer as claimed in claim 7 or 8, it also comprises: after described heat diffusion treatment, utilizes the surface of hydrofluoric acid to the n-type diffusion layer formed on a semiconductor substrate to carry out the operation of etch processes.
10. a manufacture method for solar cell device, it comprises:
Entitle requires the operation of the n-type diffusion layer formation composition described in any one in 1 ~ 6 on a semiconductor substrate;
Heat diffusion treatment is implemented to the semiconductor substrate being endowed n-type diffusion layer formation composition, thus forms the operation of n-type diffusion layer; And
Formed n-type diffusion layer is formed the operation of electrode.
CN201410050927.6A 2011-07-19 2012-07-17 N-type diffusion layer is formed by composition, the manufacture method of n-type diffusion layer and the manufacture method of solar cell device Active CN103794478B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2011158489 2011-07-19
JP2011-158489 2011-07-19
CN201280035500.8A CN103688341B (en) 2011-07-19 2012-07-17 N-type diffusion layer is formed by compositions, the manufacture method of n-type diffusion layer and the manufacture method of solar cell device

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201280035500.8A Division CN103688341B (en) 2011-07-19 2012-07-17 N-type diffusion layer is formed by compositions, the manufacture method of n-type diffusion layer and the manufacture method of solar cell device

Publications (2)

Publication Number Publication Date
CN103794478A CN103794478A (en) 2014-05-14
CN103794478B true CN103794478B (en) 2016-01-20

Family

ID=47558163

Family Applications (3)

Application Number Title Priority Date Filing Date
CN201410050927.6A Active CN103794478B (en) 2011-07-19 2012-07-17 N-type diffusion layer is formed by composition, the manufacture method of n-type diffusion layer and the manufacture method of solar cell device
CN201280035500.8A Expired - Fee Related CN103688341B (en) 2011-07-19 2012-07-17 N-type diffusion layer is formed by compositions, the manufacture method of n-type diffusion layer and the manufacture method of solar cell device
CN201510849338.9A Pending CN105489662A (en) 2011-07-19 2012-07-17 Composition that forms n-type diffusion layer, n-type diffusion layer manufacturing method and solar cell element manufacturing method

Family Applications After (2)

Application Number Title Priority Date Filing Date
CN201280035500.8A Expired - Fee Related CN103688341B (en) 2011-07-19 2012-07-17 N-type diffusion layer is formed by compositions, the manufacture method of n-type diffusion layer and the manufacture method of solar cell device
CN201510849338.9A Pending CN105489662A (en) 2011-07-19 2012-07-17 Composition that forms n-type diffusion layer, n-type diffusion layer manufacturing method and solar cell element manufacturing method

Country Status (7)

Country Link
US (1) US20150099352A1 (en)
EP (2) EP3007210A3 (en)
JP (1) JP5176159B1 (en)
KR (2) KR20140041865A (en)
CN (3) CN103794478B (en)
TW (2) TWI575762B (en)
WO (1) WO2013011986A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5176159B1 (en) * 2011-07-19 2013-04-03 日立化成株式会社 N-type diffusion layer forming composition, n-type diffusion layer manufacturing method, and solar cell element manufacturing method
JP2014179360A (en) * 2013-03-13 2014-09-25 Hitachi Chemical Co Ltd Composition for n-type diffusion layer formation, method for manufacturing semiconductor substrate having n-type diffusion layer, and method for manufacturing solar battery device
DE102013113123B4 (en) * 2013-11-27 2021-11-18 Hanwha Q Cells Gmbh Solar cell manufacturing process
DE102013113108B4 (en) * 2013-11-27 2024-08-29 Hanwha Q Cells Gmbh Solar cell manufacturing process
JP6582747B2 (en) * 2015-08-28 2019-10-02 日立化成株式会社 Composition for forming n-type diffusion layer, method for producing semiconductor substrate having n-type diffusion layer, and method for producing solar cell

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102194672A (en) * 2010-01-25 2011-09-21 日立化成工业株式会社 Composition for forming n-type diffusion layer, method for forming n-type diffusion layer, and method for producing photovoltaic cell

Family Cites Families (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE548647A (en) * 1955-06-28
US6225392B1 (en) * 1996-05-15 2001-05-01 Asahi Glass Company Ltd. Conductive paste
EP0881694A1 (en) 1997-05-30 1998-12-02 Interuniversitair Micro-Elektronica Centrum Vzw Solar cell and process of manufacturing the same
US6849334B2 (en) * 2001-08-17 2005-02-01 Neophotonics Corporation Optical materials and optical devices
US6171987B1 (en) * 1997-12-29 2001-01-09 Ben-Gurion University Of The Negev Cadmium-free and lead-free glass compositions, thick film formulations containing them and uses thereof
DE19910816A1 (en) * 1999-03-11 2000-10-05 Merck Patent Gmbh Doping pastes for producing p, p + and n, n + regions in semiconductors
US6611372B1 (en) * 2000-06-09 2003-08-26 The Arizona Board Of Regents On Behalf Of The University Of Arizona Erbium and ytterbium co-doped phosphate glass optical fiber amplifiers using short active fiber length
JP2002075894A (en) 2000-09-01 2002-03-15 Sanken Electric Co Ltd Liquid impurity source material, and semiconductor device
DE10141117A1 (en) * 2001-08-22 2003-03-13 Schott Glas Antimicrobial silicate glass and its use
DE60318517T2 (en) * 2002-04-24 2009-07-23 Central Glass Co., Ltd., Ube Lead-free low-melting glass
US7176152B2 (en) * 2004-06-09 2007-02-13 Ferro Corporation Lead-free and cadmium-free conductive copper thick film pastes
US7339780B2 (en) * 2004-06-09 2008-03-04 Ferro Corporation Copper termination inks containing lead free and cadmium free glasses for capacitors
US20060102228A1 (en) * 2004-11-12 2006-05-18 Ferro Corporation Method of making solar cell contacts
WO2006080557A1 (en) * 2005-01-31 2006-08-03 Kabushiki Kaisha Ohara Glass-ceramics and method for manufacturing the same
JP2006294579A (en) * 2005-03-17 2006-10-26 Fujitsu Ltd Manufacturing method of protruding body
US7326367B2 (en) * 2005-04-25 2008-02-05 E.I. Du Pont De Nemours And Company Thick film conductor paste compositions for LTCC tape in microwave applications
JP4481869B2 (en) * 2005-04-26 2010-06-16 信越半導体株式会社 SOLAR CELL MANUFACTURING METHOD, SOLAR CELL, AND SEMICONDUCTOR DEVICE MANUFACTURING METHOD
US7771623B2 (en) * 2005-06-07 2010-08-10 E.I. du Pont de Nemours and Company Dupont (UK) Limited Aluminum thick film composition(s), electrode(s), semiconductor device(s) and methods of making thereof
US7718092B2 (en) * 2005-10-11 2010-05-18 E.I. Du Pont De Nemours And Company Aluminum thick film composition(s), electrode(s), semiconductor device(s) and methods of making thereof
FR2906405B1 (en) * 2006-09-22 2008-12-19 Commissariat Energie Atomique METHOD OF MAKING DOPED REGIONS IN A SUBSTRATE AND PHOTOVOLTAIC CELL
JP5166745B2 (en) * 2007-03-07 2013-03-21 信越化学工業株式会社 Method for producing single crystal silicon solar cell
KR101081706B1 (en) * 2007-05-09 2011-11-09 히다치 가세고교 가부시끼가이샤 Method for connecting conductor, member for connecting conductor, connecting structure and solar cell module
KR101157771B1 (en) * 2007-05-09 2012-06-25 히다치 가세고교 가부시끼가이샤 Conductor connection member, connection structure, and solar cell module
US8309844B2 (en) * 2007-08-29 2012-11-13 Ferro Corporation Thick film pastes for fire through applications in solar cells
WO2009029738A1 (en) * 2007-08-31 2009-03-05 Ferro Corporation Layered contact structure for solar cells
JP5236914B2 (en) * 2007-09-19 2013-07-17 シャープ株式会社 Manufacturing method of solar cell
US20090092745A1 (en) * 2007-10-05 2009-04-09 Luca Pavani Dopant material for manufacturing solar cells
NL2000999C2 (en) * 2007-11-13 2009-05-14 Stichting Energie Process for the production of crystalline silicon solar cells using co-diffusion of boron and phosphorus.
KR20090080756A (en) * 2008-01-22 2009-07-27 삼성에스디아이 주식회사 A photosensitive paste composition, a barrier rib prepared using the composition and a plasma display panel comprising the barrier rib
JP5522900B2 (en) * 2008-02-22 2014-06-18 東京応化工業株式会社 Electrode forming conductive composition and method for forming solar cell
KR101631711B1 (en) * 2008-03-21 2016-06-17 신에쓰 가가꾸 고교 가부시끼가이샤 Phosphorus paste for diffusion and method for preparing solar cell by using the same
US8158504B2 (en) * 2008-05-30 2012-04-17 E. I. Du Pont De Nemours And Company Conductive compositions and processes for use in the manufacture of semiconductor devices—organic medium components
TW201007770A (en) * 2008-06-06 2010-02-16 Du Pont Glass compositions used in conductors for photovoltaic cells
CN101828267B (en) * 2008-08-07 2013-10-23 京都一来电子化学股份有限公司 Conductive paste for formation of solar cell element electrode, solar cell element, and manufacturing method for said solar cell element
US8053867B2 (en) * 2008-08-20 2011-11-08 Honeywell International Inc. Phosphorous-comprising dopants and methods for forming phosphorous-doped regions in semiconductor substrates using phosphorous-comprising dopants
KR20110137826A (en) * 2009-04-09 2011-12-23 이 아이 듀폰 디 네모아 앤드 캄파니 Glass compositions used in conductors for photovoltaic cells
JP5649290B2 (en) * 2009-07-30 2015-01-07 株式会社ノリタケカンパニーリミテド Lead-free conductive composition for solar cell electrode
JP5815215B2 (en) * 2009-08-27 2015-11-17 東京応化工業株式会社 Diffusion agent composition and method for forming impurity diffusion layer
US20110315210A1 (en) * 2009-12-18 2011-12-29 E. I. Du Pont De Nemours And Company Glass compositions used in conductors for photovoltaic cells
US20110195541A1 (en) * 2010-02-05 2011-08-11 Hitachi Chemical Company, Ltd. Composition for forming n-type diffusion layer, method for forming n-type diffusion layer, and method for producing photovoltaic cell
TWI498308B (en) * 2010-05-04 2015-09-01 Du Pont Thick-film pastes containing lead-tellurium-lithium-titanium-oxides, and their use in the manufacture of semiconductor devices
US8404599B2 (en) * 2010-11-17 2013-03-26 Hitachi Chemical Company, Ltd. Method for producing photovoltaic cell
US20120122265A1 (en) * 2010-11-17 2012-05-17 Hitachi Chemical Company, Ltd. Method for producing photovoltaic cell
EP2642527A4 (en) * 2010-11-17 2017-10-18 Hitachi Chemical Company, Ltd. Method for producing photovoltaic cell
JPWO2012067119A1 (en) * 2010-11-17 2014-05-12 日立化成株式会社 Manufacturing method of solar cell
US20120325307A1 (en) * 2010-12-16 2012-12-27 E. I. Du Pont De Nemours And Company Low bow aluminum paste with an alkaline earth metal salt additive for solar cells
WO2012127468A2 (en) * 2011-03-24 2012-09-27 Ben-Gurion University Of The Negev Research And Development Authority Coatings for solar applications
JP5176159B1 (en) * 2011-07-19 2013-04-03 日立化成株式会社 N-type diffusion layer forming composition, n-type diffusion layer manufacturing method, and solar cell element manufacturing method
US20130025670A1 (en) * 2011-07-25 2013-01-31 Hitachi Chemical Company, Ltd. Semiconductor substrate and method for producing the same, photovoltaic cell element, and photovoltaic cell
JP5856178B2 (en) * 2011-09-29 2016-02-09 株式会社ノリタケカンパニーリミテド Lead-free conductive paste composition for solar cells
WO2013125253A1 (en) * 2012-02-23 2013-08-29 日立化成株式会社 Composition for forming n-type diffusion layer, method for producing semiconductor substrate having n-type diffusion layer, and method for producing solar cell element
JP2015528178A (en) * 2012-06-12 2015-09-24 ヘレウス プレシャス メタルズ ノース アメリカ コンショホーケン エルエルシー Conductive paste with adhesion promoter
KR101999795B1 (en) * 2012-06-27 2019-07-12 삼성전자주식회사 Conductive paste and electronic device and solar cell including an electrode formed using the conductive paste

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102194672A (en) * 2010-01-25 2011-09-21 日立化成工业株式会社 Composition for forming n-type diffusion layer, method for forming n-type diffusion layer, and method for producing photovoltaic cell

Also Published As

Publication number Publication date
TW201306095A (en) 2013-02-01
EP3007210A3 (en) 2016-04-20
KR20140032492A (en) 2014-03-14
TWI575762B (en) 2017-03-21
KR20140041865A (en) 2014-04-04
TW201432919A (en) 2014-08-16
CN103688341B (en) 2016-09-28
TWI462157B (en) 2014-11-21
WO2013011986A1 (en) 2013-01-24
JPWO2013011986A1 (en) 2015-02-23
CN103688341A (en) 2014-03-26
JP5176159B1 (en) 2013-04-03
EP3007210A2 (en) 2016-04-13
KR101541660B1 (en) 2015-08-03
CN103794478A (en) 2014-05-14
CN105489662A (en) 2016-04-13
US20150099352A1 (en) 2015-04-09
EP2743967A1 (en) 2014-06-18
EP2743967A4 (en) 2015-06-03

Similar Documents

Publication Publication Date Title
TWI480930B (en) Method for producing photovoltaic cell
CN105448677A (en) Semiconductor substrate and method for producing the same, solar cell element, and solar cell
CN103794478B (en) N-type diffusion layer is formed by composition, the manufacture method of n-type diffusion layer and the manufacture method of solar cell device
CN104916531A (en) Composition that forms n-type diffusion layer, method for producing n-type diffusion layer, and method for producing solar cell element
CN104835723A (en) Composition for forming p-type diffusion layer, method for forming p-type diffusion layer, and method for producing photovoltaic cell
CN102844841B (en) N-type diffusion layer forms the manufacture method of compositions, the manufacture method of n-type diffusion layer and solar cell device
CN102959684A (en) Impurities diffusion layer forming composition, n-type diffusion layer forming composition, method for manufacturing n-type diffusion layer, p-type diffusion layer forming composition, method for manufacturing p-type diffusion layer, and method for m
CN102934205A (en) Composition for forming impurity diffusion layer, process for producing impurity diffusion layer, and process for producing solar cell element
CN102834898B (en) N-type diffusion layer forms the manufacture method of constituent, the manufacture method of n-type diffusion layer and solar cell device
CN105551947A (en) Composition for forming n-type diffusion layer, method for producing n-type diffusion layer, and method for producing solar cell element
TW201335976A (en) Composition for forming n-type diffusion layer, method of producing semiconductor substrate having n-type diffusion layer, and method of producing photovoltaic cell element
CN102859659B (en) The manufacture method of p-diffusion layer formation composition, the manufacture method of p-diffusion layer and solar cell device
CN105830200A (en) Method for manufacturing semiconductor substrate, semiconductor substrate, method for manufacturing solar cell element, and solar cell element
CN103688367A (en) Solar-cell substrate, method for manufacturing solar-cell substrate, solar-cell element, and solar cell
CN103348449A (en) Composition for forming n-type diffusion layer, process for producing n-type diffusion layer, and process for producing solar cell

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CP01 Change in the name or title of a patent holder

Address after: Tokyo, Japan

Patentee after: Showa electrical materials Co.,Ltd.

Address before: Tokyo, Japan

Patentee before: HITACHI CHEMICAL Co.,Ltd.

Address after: Tokyo, Japan

Patentee after: Lishennoco Co.,Ltd.

Address before: Tokyo, Japan

Patentee before: Showa electrical materials Co.,Ltd.

CP01 Change in the name or title of a patent holder